Compositions having a matrix and encapsulated phase change materials dispersed therein, and electronic devices assembled therewith

ABSTRACT

Provided herein are compositions made from a matrix and encapsulated phase change material particles dispersed therein, and electronic devices assembled therewith.

BACKGROUND Field

Provided herein are compositions made from a matrix and encapsulatedphase change material particles dispersed therein, and electronicdevices assembled therewith.

Brief Description of Related Technology

Thermal management materials are well known for dissipating heatgenerated by the circuitry and fans placed at strategic locations withinan electronic device also draw heat away from the circuitry, or thermalmodule. The excess heat is diverted away from the semiconductor packageto a heat sink or the thermal module with a thermal interface material(“TIM”), oftentimes disposed between the semiconductor package and theheat sink or thermal module.

However, these strategies to manage generated heat have created newproblems, as the hot air is directed away from the immediate environmentof the semiconductor package toward the interior of the housing of thedevice.

More specifically, in a conventional laptop or notebook computer (shownin FIG. 2), a housing exists under which are the components below thekeyboard (shown in FIG. 3). The components include a heat sink, a heatpipe (disposed above a CPU chip), a fan, a slot for the PCMIA card, ahard drive, a battery, and a bay for a DVD drive. The hard drive isdisposed under the left palm rest and the battery under the right.Oftentimes, the hard drive operates at high temperatures, resulting inuncomfortable palm rest touch temperatures, despite the use of coolingcomponents to dissipate this heat. This may lead to end user consumerdiscomfort due to hot temperatures attained at certain portions of theexterior of the device when the devices are used.

One solution to mute the high in use temperatures observed by the enduser at the palm rest position, for instance, is to use natural graphiteheat spreaders disposed at strategic locations. These heat spreaders arereported to distribute heat evenly while providing thermal insulationthrough the thickness of the material. One such graphite material isavailable commercially as eGraf® SpreaderShield™, from GrafTech Inc.,Cleveland, Ohio [See M. Smalc et al., “Thermal Performance Of NaturalGraphite Heat Spreaders”, Proc. IPACK2005, Interpack 2005-73073 (July,2005); see also U.S. Pat. No. 6,482,520.]

Alternative thermal management solutions are desirable and would beadvantageous, as there is a growing need in the marketplace for ways inwhich to manage the heat generated by such semiconductor packages usedin electronic devices so that end user consumers do not feel discomfortdue to the generated heat when they are used. Balanced against this needis the recognition that designers of semiconductor chips will continueto reduce the size and geometry of the semiconductor chips andsemiconductor packages but increase their computing capacity. Thecompeting interests of size reduction and increased computing power makethe electronic devices appealing for the consumer, but in so doingcauses the semiconductor chips and semiconductor packages to continue tooperate at elevated temperature conditions, and indeed increasingelevated temperature conditions. Accordingly, it would be advantageousto satisfy this growing need with alternative technologies to encouragethe design and development of even more powerful consumer electronicdevices, which have reduced “skin temperature” and as such are not hotto the touch in operation.

SUMMARY

Provided herein is a composition including a matrix within which isdispersed a plurality of encapsulated phase change material particles.The composition is capable of absorbing heat. As such, in use it may bedisposed onto at least a portion of a surface of a heat spreading deviceconstructed from conductive materials, such as metal or metal-coatedpolymeric substrate, or graphite or metal-coated graphite, examples ofwhich include Cu, Al, and graphite, and Cu- or Al-coated graphite.

The matrix of the composition may be a resin based one, such as apressure sensitive adhesive (“PSA”), as those adhesives are commonlyreferred to, or an acrylic emulsion.

Where the matrix is a PSA, the composition may be disposed onto at leasta portion of a surface of a heat spreading device to provide both EMIshielding and to enhance thermal performance of such device.

The composition may also function as a thermal absorber film for use ina transfer tape format so that the composition may be applied to anylocation on the device that requires cooling, such as on the interior ofan EMI shield. Desirably, in such use, the encapsulated phase changematerial is coated on at least a portion of the surface thereof with ametal coating.

Where the matrix is an acrylic emulsion, the composition may likewise beso dispersed. However, the carrier liquid of the emulsion is evaporatedprior to placing the composition under operating conditions.

The composition may be disposed onto a substrate or between twosubstrates. The substrate(s) may serve as a support or may serve as aheat spreader, in which case the support may be constructed from aconductive material which is a metal or a metal-coated polymericsubstrate, or graphite or a metal-coated graphite.

The composition may be used with an article, such as a power source likea battery module to dissipate heat generated by the power source duringoperation. That operating temperature may be as high as about 40° C. Inthis embodiment, a housing comprising at least one substrate having aninterior surface and an exterior surface is provided over and/or aboutthe article and on an interior facing surface thereof, and a compositioncomprising a plurality of encapsulated phase change material particlesdispersed within a matrix disposed upon a substrate, which as notedabove may serve as a support or provide thermal conductivity to aid inspreading the generated heat, is disposed on at least a portion of theinterior surface of the at least one substrate. In one aspect theencapsulated phase change material particles may have a layer of aconductive material disposed on at least a portion of the surface of theparticles. The conductive coating should be metallic such as Ag, Cu orNi so as to provide an EMI shielding effect.

In an embodiment for use in a consumer electronic article ofmanufacture, a housing is provided which comprises at least onesubstrate having an interior surface and an exterior surface; acomposition is provided which comprises a plurality of encapsulatedphase change material particles dispersed within a matrix disposed upona substrate, which as noted above may serve as a support or providethermal conductivity to aid in spreading the generated heat, which layeris disposed on at least a portion of the interior surface of the atleast one substrate; and at least one semiconductor package is providedwhich comprises an assembly comprising at least one of

I.

-   -   a semiconductor chip;    -   a heat spreader; and    -   a thermal interface material therebetween (also known as a TIM1        application)        II.    -   a heat spreader;    -   a heat sink; and    -   a thermal interface material therebetween (also known as a TIM2        application).

Also, provided herein is a method of manufacturing such a consumerelectronic device.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a cut away view of a circuit board on which is disposed aplurality of semiconductor packages and circuitry, together withelectronic materials ordinarily used in the assembly of the packagesthemselves and the assembly of the packages onto the board. Referencenumbers 1-18 refer to some electronic materials used in the packagingand assembly of semiconductors and printed circuit boards.

FIG. 2 depicts a laptop personal computer in the open position.

FIG. 3 depicts a top view of the contents of the laptop personalcomputer, beneath the keyboard and palm rests thereof.

FIG. 4 depicts a general schematic diagram of an electronic device.

FIG. 5 depicts a plan view of the locations for skin temperaturemeasurements in a tablet.

FIGS. 6A-B shows a representation of the compositional layers of athermal absorbing film, where (A) a composition including a matrixwithin which is dispersed a plurality of encapsulated phase changematerial particles (61) is placed in contact with a conductive support(62) and (B) a composition including a matrix within which is disperseda plurality of metal-coated encapsulated phase change material particles(63) is placed in contact with a conductive support (64), to form an EMIshielding thermal absorbing film.

FIG. 7 depicts a top view within the housing of a tablet of a powermodule under which the inventive composition (not shown) is disposed.

DETAILED DESCRIPTION

As noted above, provided herein is a composition including a matrixwithin which is dispersed a plurality of encapsulated phase changematerial particles. The composition may be disposed onto a substrate orbetween two substrates. The substrate(s) may serve as a support or mayserve as a heat spreader, in which case the support may be constructedfrom a conductive material which is metal or metal-coated polymericsubstrate, or graphite or a metal-coated graphite.

The composition comprises a matrix (such as a PSA or an acrylicemulsion), in which is dispersed an encapsulated PCM. Optionally, thecomposition may also include thermally insulative elements. In oneembodiment, a metallic or graphite substrate may be used as a support onwhich the composition is disposed. In this way the metallic or graphitesubstrate may acts as a heat spreader to further dissipate heat.

The composition—i.e., the PSA in which is dispersed an encapsulatedPCM—may be coated on a heat spreading device, such as a metal like Cu orAl, graphite, or a metal-coated graphite—to enhance thermal performanceof such devices.

The composition may be coated on a heat spreading device to also provideEMI shielding as well as to enhance thermal performance of such devices.

In the form of a transfer tape, the composition as a thermal absorberfilm may be applied to any location that requires cooling, such asinside the EMI shield. See e.g. FIG. 6.

The composition may be used with an article, such as a power source likea battery module to dissipate heat generated by the power source duringoperation. That operating temperature may be as high as about 40° C. Inthis embodiment, a housing comprising at least one substrate having aninterior surface and an exterior surface is provided over and/or aboutthe article and on an interior facing surface thereof a compositioncomprising a plurality of encapsulated phase change material particlesdispersed within a matrix disposed upon a substrate, which as notedabove may serve as a support or provide thermal conductivity to aid inspreading the generated heat, is disposed on at least a portion of theinterior surface of the at least one substrate. In one aspect theencapsulated phase change material particles may have a layer of aconductive material disposed on at least a portion of the surface of theparticles. The conductive coating should be metallic, such as Ag, Cu orNi, so as to provide an EMI shielding effect.

In an embodiment for use in a consumer electronic article ofmanufacture, a housing is provided which comprises at least onesubstrate having an interior surface and an exterior surface; acomposition is provided which comprises a plurality of encapsulatedphase change material particles dispersed within a matrix disposed upona substrate, which as noted above may serve as a support or providethermal conductivity to aid in spreading the generated heat, which layeris disposed on at least a portion of the interior surface of the atleast one substrate; and at least one semiconductor package is providedwhich comprises an assembly comprising at least one of

I.

-   -   a semiconductor chip;    -   a heat spreader; and    -   a thermal interface material therebetween (also known as a TIM1        application)        II.    -   a heat spreader;    -   a heat sink; and    -   a thermal interface material therebetween (also known as a TIM2        application).

The composition may be used in the assembly of a consumer electronicarticle of manufacture. This article of manufacture (or “device”) may beselected from notebook personal computers, tablet personal computers orhandheld devices, for instance, music players, video players, stillimage players, game players, other media players, music recorders, videorecorders, cameras, other media recorders, radios, medical equipment,domestic appliances, transportation vehicle instruments, musicalinstruments, calculators, cellular telephones, other wirelesscommunication devices, personal digital assistants, remote controls,pagers, monitors, televisions, stereo equipment, set up boxes, set-topboxes, boom boxes, modems, routers, keyboards, mice, speakers, printers,and combinations thereof.

The device may also include a venting element to disperse heat generatedfrom the semiconductor assembly away from the device.

Of course, the consumer electronic device is provided with a powersource to energize the semiconductor package(s).

The semiconductor package may be formed with a die attach materialdisposed between a semiconductor chip and a circuit board to securelyadhere the chip to the board. Wire bonding forms the electricalinterconnection between the chip and the board. This die attach materialis oftentimes a highly filled material with a thermosetting resinmatrix. The matrix may be composed of epoxy, maleimide, itaconimide,nadimide and/or (meth)acrylate. The filler may be conductive ornon-conductive. In some instances, the die attach material is thermallyconductive, in which case it too aids in dissipating heat away from thesemiconductor package. Representative commercially available examples ofsuch die attach materials include QMI519HT from Henkel Corporation.

Alternatively, the semiconductor package may be formed with asemiconductor chip electrically connected to a circuit board with solderinterconnects in a space therebetween. In that space an underfillsealant may be disposed. The underfill sealant will also have athermosetting matrix resin, which like the die attach material may becomposed of epoxy, maleimide, itaconimide, nadimide and/or(meth)acrylate. The underfill sealant is ordinarily also filled.However, the filler is generally non-conductive and used for the purposeof accommodating differences in the coefficients of thermal expansion ofthe semiconductor die and the circuit board. Representative commerciallyavailable examples of such underfill sealants include HYSOL FP4549HTfrom Henkel Corporation.

Once the semiconductor package has been positioned onto the circuitboard and attached thereto oftentimes by a surface mount adhesive, achip bonder, or chip scale package underfill sealant, the package may beovermolded with mold compound in order to protect the package from amongother things environmental contaminants. The mold compound is oftentimesepoxy based, but may also contain benzoxazine and/or other thermosetresins. GR750 is an example of an epoxy mold compound, availablecommercially from Henkel Corporation, designed to improve thermalmanagement in semiconductor devices.

Solder pastes are used at various portions on the circuit board toattach semiconductor packages and assemblies, in an electricallyinterconnected manner. One such solder paste is available commerciallyfrom Henkel Corporation under the tradename MULTICORE Bi58LM100. Thislead free solder paste is designed for applications where thermalmanagement is desirable.

To effectively manage the heat generated by semiconductor chips andsemiconductor packages, a thermal interface material may be used withany heat-generating component for which heat dissipation is required,and in particular, for heat-generating components in semiconductordevices. In such devices, the thermal interface material forms a layerbetween the heat-generating component and the heat sink and transfersthe heat to be dissipated to the heat sink. The thermal interfacematerial may also be used in a device containing a heat spreader. Insuch a device, a layer of thermal interface material is placed betweenthe heat-generating component and the heat spreader, and a second layerof thermal interface material is placed between the heat spreader andthe heat sink.

The thermal interface material may be a phase change material, such asone commercially available from Henkel Corporation under the tradenamesPOWERSTRATE EXTREME, PowerstrateXtreme or PSX. Packaged as afree-standing film between two release liners and supplied as a die cutperform to match a wide variety of applications, this thermal interfacematerial is a reworkable phase change material suitable for use forinstance between a heat sink and variety heat dissipating components.The material flows at the phase change temperature, conforming to thesurface features of the components. The thermal interface material whenin the form of a phase change material has a melting point ofapproximately 51° C. or 60° C.

Upon flow, air is expelled from the interface, reducing thermalimpedance, performing as a highly efficient thermal transfer material.

The thermal interface material may be constructed from (a) 60% to 90% byweight of paraffin; (b) 0% to 5% by weight of resin; and (c) 10% to 40%by weight of metal particle, such as an electrically-conductive filler.The electrically-conductive filler is ordinarily one selected fromgraphite, diamond, silver, and copper. Alternatively, theelectrically-conductive filler may be aluminum, such as a sphericalalumina.

The metal particles suitable for use in the thermal interface materialmay be fusible metal particles, typically low melting point metals ormetal alloys used as solders. Examples of such metals include bismuth,tin, and indium, and may also include silver, zinc, copper, antimony,and silver coated boron nitride. In one embodiment the metal particlesare selected from tin, bismuth, or both. In another embodiment, indiumwill also be present. Alloys of the above metals also can be used.

An eutectic alloy of tin and bismuth powder (melting point 138° C.), ina weight ratio of tin to bismuth of Sn48Bi52 may also be used,particularly in combination with indium powder (melting point 158° C.),in which the indium is present in a weight ratio of 1:1 with the Sn:Bialloy.

The metal particles and/or alloys should be present in the compositionin a range from 50 to 95 weight percent of the thermal interfacematerial.

The thermal interface material may also be a thermal grease, such as onecommercially available from Henkel Corporation under the tradedesignations TG100, COT20232-3611 or COT20232-36E1. TG100 is a thermalgrease designed for high-temperature heat transfer. In use, TG100 isplaced between heat generating devices and the surfaces to which theyare mounted or other heat dissipating surfaces. This product deliversexcellent thermal resistance, offers high thermal conductivity andvirtually no evaporation over a wide operating temperature range. Inaddition, COT20232-36E1 and COT20232-36I1 are TIM1 type materials,designed in this instance for high power flip chip applications. Theseproducts contain a soft gel polymer or curable matrix, which after cureforms an interpenetrating network with a low melting point alloytherewithin. The low melting point alloy may be fusible metal solderparticles, particularly those substantially devoid of added lead,comprising an elemental solder powder and optionally a solder alloy.

The thermal interface material in use should have a thermal impedance ofless than 0.2 (° C. cm²/Watt).

The housing comprises at least two substrates and oftentimes a pluralityof substrates. The substrates are dimensioned and disposed to engage oneanother. In order to manage the heat that may emanate from the interiorof a consumer electronic device, and control the so called “skintemperature”, it is oftentimes desirable to place between the housingand the semiconductor devices that generate heat a thermal managementsolution.

Here, that solution is a heat absorbing and/or thermally insulatingcomposition, which more specifically is a phase change material (“PCM”)that has been encapsulated within a shell, dispersed within a matrix,such as a pressure sensitive adhesive. For a general review ofencapsulated PCMB, see e.g. Pramod B. Salunkhe et al., “A review oneffect of phase change material encapsulation on the thermal performanceof a system”, Renewable and Sustainable Energy Reviews, 16, 5603-16,(2012).

PCMs may be composed of organic or inorganic materials. For instance,organic materials useful in PCMs include paraffin, fatty acids, esters,alcohols, glycols, or organic eutectics. And petrolatum, beeswax, palmwax, mineral waxes, glycerin and/or certain vegetable oils may also beused. Inorganic materials useful in PCMs include salt hydrates and lowmelting metal eutectics. The paraffin may be a standard commercial gradeand should include a paraffin wax having a melting point below about 40°C. Use of such a paraffin wax permits the matrix to transition from itssolid to liquid state at a temperature below about 37° C. In addition toparaffin, as noted above, petrolatum, beeswax, palm wax, mineral waxes,glycerin and/or certain vegetable oils may be used to form a PCM. Forinstance, the paraffin and petrolatum components may be blended togethersuch that the ratio of such components (i.e., paraffin to petrolatum) isbetween approximately 1.0:0 to 3.0:1% by weight. In this regard, as thepetrolatum component is increased relative say to the paraffincomponent, the PCM should increase in softness.

Commercially available representative PCMs include MPCM-32, MPCM-37,MPCM-52 and Silver Coated MPCM-37, where the number represents thetemperature at which the PCM changes phase from solid to liquid.Suppliers include Entropy Solutions Inc., Plymouth, Minn. whose PCMs aresold under the Puretemp tradename and Microtek Laboratories, Inc.,Dayton, Ohio. Microtek describes the encapsulated PCMs as consisting ofan encapsulated substance with a high heat of fusion. The phase changematerial absorbs and releases thermal energy in order to maintain aregulated temperature within a product such as textiles, buildingmaterials, packaging, and electronics. The capsule wall or shellprovides a microscopic container for the PCM. Even when the core is inthe liquid state, the capsules still act as a solid—keeping the PCM from“melting away.”

The PCM itself should be such that a phase change from solid ornon-flowable to liquid or flowable occurs within a given temperaturerange.

In order to select a PCM for a specific application, the operatingtemperature of the device should be matched to the transitiontemperature of the PCM. PCMs for use herein should have a melting rangewithin the range of about 30° C. to about 100° C., and all 2° C. and 5°C. increments within that range. When the PCMs are to be used with powermodules a melting temperature of less than about 40° C. is desirable asthat is the temperature vicinity in which the power modules ordinarilyoperate. When the PCMs are to be used with computer processing units(“CPU”) a melting temperature in the range of about 50° C. to about 90°C. is desirable as that is the temperature range in which the CPUordinarily operate.

Advantageously, the melting point of the constituents used in the PCM isselected to be below the temperature at which the devices operate. Inthis regard, a PCM in which a paraffin component is used assumes aliquid state during the operation of the consumer electronic device, andonly during such time as the device operates at such elevatedtemperatures. As a result, heat absorption and release is modulatedbetween the liquid and solid states, respectively, across the operatingtemperature range of the consumer electronic device in which the presentinvention is placed. This assists in modulating the “skin” temperatureof the consumer electronic device, so as to minimize the temperaturethat the end user experiences when the consumer electronic device is inuse.

As the PCM matrix undergoes its phase transition from a solid to aliquid state, the matrix absorbs heat until the matrix is transformedinto the liquid state, which in this case at the operating temperatureof the consumer electronic device is ordinarily a gel like state.

As the PCM matrix changes from a liquid to a solid state; the liquidstate releases the absorbed heat until the matrix is transformed intosolid state.

The melting temperature of the PCM matrix should be in the desiredoperating temperature range of the consumer electronic device.

The PCM matrix should also have a high latent heat of diffusion.

The PCM matrix should not degrade after multiples freeze-melt cycles.

The PCMs are dispersed in a matrix, which may be a pressure sensitiveadhesive (“PSA”) or an acrylic emulsion. The PSA is ordinarily made fromacrylic polymers, such as those having the following composition orthose that can be prepared by polymerizing (i) an acrylic monomer whichis an acrylic or methacrylic acid derivative (e.g. methacrylic acidester) of the formula CH₂═CH(R¹)(COOR²), where R¹ is H or CH₃ and R² isa C₁₋₂₀, preferably C₁₋₈, alkyl chain and (ii) a monomer with a pendantreactive functional group, which is described in more detail hereinbelow, and the amount of the monomer (ii) is from about 0.001 to about0.015 equivalent per 100 g of the acrylic polymer. See e.g. C. Houtmanet al., “Properties of Water-based Acrylic Pressure Sensitive AdhesiveFilms in Aqueous Environments”, 2000TAPPI Recycling Symposium,Washington, D.C. (5-8 Mar. 2000).

For the polymerization process, the monomers of components (I) and (ii),where appropriate, are converted by radical polymerization into acrylicpolymers. The monomers are chosen such that the resulting polymers canbe used to prepare PSAs in accordance with D. Satas, “Handbook ofPressure Sensitive Adhesive Technology”, van Nostrand, NY (1989).

Examples of acrylates and/or methacrylates useful as components ofmonomer mixture (i) include methyl acrylate, ethyl acrylate, ethylmethacrylate, methyl methacrylate, n-butyl acrylate, n-butylmethacrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate,and n-octyl acrylate, n-nonyl acrylate, lauryl methacrylate, cyclohexylacrylate, and branched (meth)acrylic isomers, such as i-butyl acrylate,i-butyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate,stearyl methacrylate, and isooctyl acrylate.

The exemplary acrylic monomer mixture (i) has a Tg value less than 0° C.and a weight average molecular weight from about 10,000 to about2,000,000 g/mol, such as between 50,000 and 1,000,000 g/mol anddesirably between 100,000 and 700,000 g/mol. The mixture (i) may be asingle monomer provided that it has a homopolymer Tg of less than 0° C.

Examples of suitable monomer (ii) are those capable of providing greenstrength to the adhesive films, include cycloaliphatic epoxide monomersM100 and A400 (Daicel), oxetane monomer OXE-10 (available commerciallyfrom Kowa Company), dicyclopentadienyl methacrylate epoxide (CD535,available commercially from Sartomer Co., Exton, Pa.), and4-vinyl-1-cyclohexene-1,2-epoxide (available commercially from Dow).

The acrylic polymers are capable of undergoing post-UV cationicactivated reaction and thus, provide high temperature holding strengthto the adhesive films. The acrylic polymers are those having thefollowing composition or those that can be prepared by polymerizing (i)an acrylic monomer which is an acrylic or methacrylic acid derivative ofthe formula CH₂═CH(R₁)(COOR₂), where R₁ is H or CH₃ and R₂ is C₁₋₂₀alkyl chain and (ii) a monomer with a combination of pendant reactivefunctional groups selected from both (1) cycloaliphatic epoxide,oxetane, benzophenone or mixtures thereof, and (2) mono-substitutedoxirane. The amount of monomer (ii) is about 0.001 to about 0.015equivalent per 100 g of the acrylic polymer. The acrylic polymer isessentially free of multi-(meth)acrylate, polyol or OH-functional groupsand the polymer remains substantially linear after polymerization. In amore preferred embodiment, the amount of the monomer (ii) is from about0.002 to about 0.01 equivalent per 100 g of the acrylic polymer.

The acrylic polymers prepared generally have a weight averaged averagemolecular weight (M_(w)) of from 10,000 to 2,000,000 g/mol, such asbetween 50,000 and 1,000,000 g/mol, like between 100,000 and 700,000g/mol. M_(w) is determined by gel permeation chromatography ormatrix-assisted laser desorption/ionization mass spectrometry.

Examples of mono-substituted oxiranes useful as monomer (ii) includeglycidyl methacrylate, 1,2-epoxy-5-hexene, 4-hydroxybutylacrylateglycidyl ether, cycloaliphatic epoxide monomer M100 and A400, OXE-10,CD535 epoxide, and 4-vinyl-1-cyclohexene-1,2-epoxide.

The PSA may also comprise various other additives, such as plasticizers,tackifiers, and fillers, all of which are conventionally used in thepreparation of PSAs. As plasticizers to be added, low molecular weightacrylic polymers, phthalates, benzoates, adipates, or plasticizerresins, are but a few possibilities. As tackifier or tackifying resinsto be added, it is possible to use any known tackifying resins describedin the literature. Non-limiting examples include pinene resins, indeneresins, and their disproportionated, hydrogenated, polymerized, andesterified derivatives and salts, the aliphatic and aromatic hydrocarbonresins, terpene resins, terpene-phenolic resins, C₅ resins, C₉ resins,and other hydrocarbon resins. Any desired combinations of these or otherresins may be used in order to adjust the properties of the resultantadhesive in accordance with the desired final properties.

The PSAs may further be blended with one or more additives such as aginginhibitors, antioxidants, light stabilizers, compounding agents, and/oraccelerators.

Commercial representative examples of suitable PSAs include thoseavailable from Henkel Corporation under the trade name DUROTAK.

The inventive compositions include:

a matrix, such as in an amount of 10% to 80% by volume; and

encapsulated PCM, such as in an amount of 20% to 90% by volume; and

optionally, thermally insulative elements.

It may be desirable to include thermal insulating elements to theencapsulated PCM-containing matrix. Representative commerciallyavailable examples of such thermal insulators include hollow sphere-likevessels, such as those sold under the DUALITE tradename by HenkelCorporation or the EXPANCEL tradename by Akzo Nobel, such as DUALITE E.DUALITE E is promoted to lower the thermal conductivity of the finalproduct in which it is used as cost reducing or weight saving component.Using DUALITE E is reported to introduce stable, hollow, closed-cellvoids into the final product.

In addition, solid materials having porosity or interstices in which gasis disposed may be used as an alternative to or in combination with thehollow sphere-like vessels. The thermally insulating elements in thisregard may comprise a gas disposed within interstices of a substantiallysolid sphere-like particle. Representative commercially availableexamples of such thermally insulating elements include those sold underthe AEROGEL NANOGEL tradename by Degussa Corporation. They are describedby the manufacturer as lightweight, insulating silica materials,composed of a lattice network of glass strands with very small pores,composed from up to 5% solids and 95% air. This structure, it isreported, creates superior insulating, light transmitting and waterrepelling properties. The silica materials are a nanoporous silica withan average pore size of 20 nanometers. The small pore size and structuretraps the flow of air to prevent heat loss and solar heat gain.

When used, the thermal insulating element(s) are disposed in a matrix ata concentration of 25% to 99% by volume in the matrix to form a heatabsorbing and/or thermally insulating composition.

The inventive composition may be disposed as a layer or coating on atleast a portion of the surface of the substrate. The so-formed coatingis thick enough to aid in creating a barrier to heat transmissionthrough the substrate from the heat generated from the semiconductorpackages when in use, but not so thick so as to interfere with theassembly and/or operation of the consumer electronic device.

The inventive compositions should be disposed on at least a portion ofthe interior surface of the at least one substrate that comprises thehousing, the complementary exterior surface of which comes into contactwith the end user when in use. So, with reference to FIG. 2, palm restswould be good examples of this location on a lap top or notebookpersonal computer.

With reference to FIG. 1, a cut way view of a circuit board is shown. Onthe circuit board is disposed a plurality of semiconductor packages andcircuitry, together with electronic materials ordinarily used in theassembly of the packages themselves and the assembly of the packagesonto the board, and a portion of the housing of the electronic device inwhich the circuit board is to be used. In FIG. 1, 1 refers to surfacemount adhesives (such as LOCTITE 3609 and 3619); 2 refers to thermalinterface materials, as described in more detail herein; 3 refers to lowpressure molding materials (such as MM6208); 4 refers to flip chip onboard underfill such as HYSOL FP4531); 5 refers to liquid encapsulantsglob top (such as HYSOL E01016 and E01072); 6 refers to siliconeencapsulants (such as LOCTITE 5210); 7 refers to gasketing compounds(such as LOCTITE 5089); 8 refers to a chip scale package/ball grid arrayunderfill (such as HYSOL UF3808 and E1216); 9 refers to a flip chip airpackage underfill (such as HYSOL FP4549 HT); 10 refers to coating powder(such as HYSOL DK7-0953M); 11 refers to mechanic molding compound (suchas HYSOL LL-1000-3NP and GR2310); 12 refers to potting compound (such asE&C 2850FT); 13 refers to optoelectronic (such as Ablestik AA50T); 14refers to die attach (such as Ablestick 0084-1LM1SR4, 8290 and HYSOLOMI529HT); 15 refers to conformal coating (such as LOCTITE 5293 andPC40-UMF); 16 refers to photonic component and assembly materials (suchas STYLAST 2017M4 and HYSOL OT0149-3); 17 refers to semiconductor moldcompound; and 18 refers to solder (such as Multicore BI58LM100AAS90V and97SCLF318AGS88.5). Each of these products is available for salecommercially from Henkel Corporation, Irvine, Calif.

The circuit board A of FIG. 1 is disposed within the interior of thehousing of an electronic device (not shown). On at least a portion of aninwardly facing surface of a substrate which comprises the housing ofthe electronic device is coated a layer of thermally insulating elements(not shown).

As shown in FIG. 4, electronic device 100 may include housing 101,processor 102, memory 104, power supply 106, communications circuitry108-1, bus 109, input component 110, output component 112, and coolingcomponent 118. Bus 109 may include one or more wired or wireless linksthat provide paths for transmitting data and/or power, to, from, orbetween various components of electronic device 100 including, forexample, processor 102, memory 104, power supply 106, communicationscircuitry 108-1, input component 110, output component 112, and coolingcomponent 118.

Memory 104 may include one or more storage mediums, including, but notlimited to, a hard-drive, flash memory, permanent memory such asread-only memory (“ROM”), semi-permanent memory such as random accessmemory (“RAM”), any other suitable type of storage component, and anycombinations thereof. Memory 104 may include cache memory, which may beone or more different types of memory used for temporarily storing datafor electronic device applications.

Power supply 106 may provide power to the electronic components ofelectronic device 100, either by one or more batteries or from a naturalsource, such as solar power using solar cells.

One or more input components 110 may be provided to permit a user tointeract or interface with device 100, such as by way of an electronicdevice pad, dial, click wheel, scroll wheel, touch screen, one or morebuttons (e.g., a keyboard), mouse, joy stick, track ball, microphone,camera, video recorder, and any combinations thereof.

One or more output components 112 can be provided to present information(e.g., textual, graphical, audible, and/or tactile information) to auser of device 100, such as by way of audio speakers, headphones, signalline-outs, visual displays, antennas, infrared ports, rumblers,vibrators, and any combinations thereof.

One or more cooling components 118 can be provided to help dissipateheat generated by the various electronic components of electronic device100. These cooling components 118 may take various forms, such as fans,heat sinks, heat spreaders, heat pipes, vents or openings in housing 101of electronic device 100, and any combinations thereof.

Processor 102 of device 100 may control the operation of many functionsand other circuitry provided by device 100. For example, processor 102can receive input signals from input component 110 and/or drive outputsignals through output component 112.

Housing 101 should provide at least a partial enclosure to one or moreof the various electronic components that operate electronic device 100.Housing 100 protects the electronic components from debris and otherdegrading forces external to device 100. Housing 101 may include one ormore walls 120 that define a cavity 103 within which various electroniccomponents of device 100 can be disposed. Housing openings 151 may alsoallow certain fluids (e.g., air) to be drawn into and discharged fromcavity 103 of electronic device 100 for helping to manage the internaltemperature of device 100. Housing 101 can be constructed from a varietyof materials, such as metals (e.g., steel, copper, titanium, aluminum,and various metal alloys), ceramics, plastics, and any combinationsthereof.

Rather than being provided as a single enclosure, housing 101 may alsobe provided as two or more housing components. Processor 102, memory104, power supply 106, communications circuitry 108-1, input component110, and cooling component 118 may be at least partially containedwithin a first housing component 101 a, for instance, while outputcomponent 112 may be at least partially contained within a secondhousing component 101 b.

With respect to a power module assembly, the composition may be disposedon a surface of a power module. For instance, a power module assembly isprovided, which comprises a power module having at least two surfaces,and a composition comprising a plurality of encapsulated phase changematerial particles dispersed within a matrix disposed upon at least aportion of one of the surfaces.

EXAMPLES

The constituents listed in Table 1 below were placed in a vessel withstirring to form a mixture.

TABLE 1 Sample Nos./Amt (wt %) Constituents 1 2 3 4 5 6 7 8 COVINAX 331Acrylic 66 66 66 60 emulsion^($) GELVA GME 3011^(✓) 66 60 DUROTAK151A^(#) 66 DUROTAK 1068* 66 MPCM-32 34 MPCM-37 34 34 34 34 MPCM-52 34Silver Coated MPCM-37 40 40 ^($)COVINAX 331-00 is available commerciallyfrom Franklin Adhesives and Polymers and is described as a surfactantstabilized acrylic copolymer, which was developed for permanent pressuresensitive applications requiring high tack and peel strength. Accordingto the manufacturer, COVINAX 331-00 exhibits excellent adhesion tocorrugated board, polyolefin films and most types of foams; formspermanent bonds whether at room temperature or refrigeratortemperatures; and its wide adhesion range allows it to be used in avariety of different applications, including all temperature gradelabels. ^(✓)GELVA GME 3011 is a solution rubber based PSA and isavailable from Henkel Corporation. ^(#)DUROTAK 151A is a solutionacrylic pressure sensitive adhesive designed for applications requiringrapid wet-out and high tack on low energy surfaces. The reportedphysical properties include: tack (in ozf/in) (81), peel strength (inozf/in): from stainless steel after 20 minutes (85), 24 hours (96), oneweek at room temperature (96), one week at 158° F. (115), and one weekat 95° F./95% RH (105), and from HDPE after 20 minutes (45) and after 24hours (47), and shear strength at 72° F. after 1 hour (10) (4.4 psi)*DUROTAK 1068 is a solution acrylic pressure sensitive adhesive designedfor general purpose transfer film and high heat applications. Thereported physical properties include: tack (in ozf/in) (45), peelstrength (in ozf/in): from stainless steel after 20 minutes (60), 24hours (78), one week at room temperature (94), one week at 158° F.(145), and one week at 95° F./95% RH (110), and from HDPE after 20minutes (13) and after 24 hours (20), and shear strength at 72° F. after1 hour (11) (8.8 psi)

MPCM materials were purchased from Microtek Laboratories. The materialshave a core of one or material(s) that melts at the given temperature(in ° C.). For instance, MPCM-32 is a special blend, whereas MPCM-37 isn-eicosane. Silver Coated MPCM-37 has a silver coating that is about 1μm thick

Each mixture was stirred for a period of time of 60 minutes to dispersethe encapsulated phase change materials and form the numbered samples.

A 0.03 mm coating of each sample coated on 25 um thick graphite film asillustrated in FIGS. 6A-B. The composite sample was placed on a testdie, and exposed to a temperature of 50° C. to produce a temperaturedrop of 6-8° C. A composition prepared in a similar manner thoughwithout the encapsulated phase change materials and likewise placed on atest die produced a temperature drop of about 2-3° C.

In Table 2 below, Sample Nos. 1-8 were placed at the top of the CPUlocation shown on a tablet in FIG. 7, and the following measuredproperties were recorded and are listed in the leftmost column.Reference to FIG. 7 shows such a power module 71 within the interior ofa tablet 7 and a CPU 72 in proximity thereto. The values shown are theCPU temperature and highest skin temperature. The values for Sample Nos.1-8 are presented.

One set of controls used a graphite heat spreader and another set ofcontrols was disposed directly on the tablet computer processing unit.

TABLE 2 Physical Sample Nos. Properties 1 2 3 4 5 6 7 8 Solids, % 70.370.3 70.3 73.6 73 73 70 70 PCM melting 32 37 52 37 37 37 37 37 point, °C. Heat of fusion, 55 75 70 60 108 110 95 90 J/cc Peel Adhesion 2.5 32.5 2.2 2.8 3 2.5 2.2 (25 um dry film coated on 50 um Cu foil), lbMeasured CPU 72 71 70 72 72 71 71 71 Temperature, ° C. Highest Skin 41.841.5 40.0 41.8 41.0 40.6 41.2 41.5 temperature, ° C.

The CPU temperature for each of the two controls—graphite and directapplication—was measured at 74° C. and 78° C., respectively. Themeasurements were taken directly from the tablet itself. Thus, adramatic reduction—as high as about 11%—may be realized.

The measured skin temperature for each of the two controls, graphite andnothing, was 42° C. and 45° C. Each of Sample Nos. 1-8 performed betterthan the control graphite heat spreader, which was approximately 10%better than with no heat spreader at all.

What is claimed is:
 1. A consumer electronic article of manufacturecomprising: a housing comprising at least one housing substrate havingan interior surface and an exterior surface; a combination comprising acomposition and a substrate on which the composition is disposed, thecomposition comprising a matrix and encapsulated phase change materialparticles dispersed therein, wherein: the matrix comprises a pressuresensitive adhesive or an acrylic emulsion, the encapsulated phase changematerial has a melting point in the range of about 30° C. to about 100°C., the composition comprises: about 10 to about 80% by volume of thematrix and about 20 to about 90% by volume of the encapsulated phasechange material, the substrate is selected from the group consisting ofa metallic, a metal-coated polymeric, a graphite or a metal-coatedgraphitic substrate, on which the composition is disposed, and whereinthe combination is disposed on at least a portion of the interiorsurface of the at least one housing substrate; and at least onesemiconductor package comprising an assembly comprising at least one ofI. a semiconductor chip; a heat spreader; and a thermal interfacematerial therebetween, or II. a heat spreader; a heat sink; and athermal interface material therebetween.
 2. The article of claim 1,further comprising a venting element to disperse generated heat from thesemiconductor assembly from the article.
 3. The article of manufactureof claim 1, wherein the housing comprises at least two substrates. 4.The article of manufacture of claim 1, wherein the housing comprises aplurality of substrates.
 5. The article of manufacture of claim 1,wherein the substrates are dimensioned and disposed to engage oneanother.
 6. The article of manufacture of claim 1, wherein thecomposition is disposed on at least a portion of the interior surface ofthe at least one housing substrate, the complementary exterior surfaceof which comes into contact with the end user when in use.
 7. Thearticle of manufacture of claim 1, wherein the composition furthercomprises thermally insulating materials.
 8. The article of manufactureof claim 7, wherein the thermally insulating materials in thecomposition comprise a gas.
 9. The article of manufacture of claim 7,wherein the thermally insulating materials in the composition compriseair.
 10. The article of manufacture of claim 7, wherein the thermallyinsulating materials in the composition comprise a gas within a hollowsphere-like vessel.
 11. The article of manufacture of claim 7, whereinthe thermally insulating materials are used at a concentration withinthe range of 25% to 99% by volume in the composition.
 12. The article ofmanufacture of claim 1, wherein the composition facilitates the transferof heat from an electronic component to a heat sink.
 13. The article ofmanufacture of claim 1, wherein the thermal interface material has amelting point of approximately 37° C.
 14. The article of manufacture ofclaim 1, wherein the encapsulated phase change material has a meltingpoint of approximately 37° C.
 15. The article of manufacture of claim 1,wherein the thermal interface material has a melting point ofapproximately 52° C.
 16. The article of manufacture of claim 1, whereinthe encapsulated phase change material has a melting point ofapproximately 52° C.
 17. The article of manufacture of claim 1, whereinthe article is a notebook personal computer, tablet personal computer ora handheld device.